Metal–organic frameworks (MOFs) with open metal sites (OMS) are known to have selectivity in olefin/paraffin separations because of π–π interactions between olefin double bonds and OMS. One challenge associated with these separations is that other species that potentially bind to OMS may also be present in feed streams, causing competition for these sites. We used density functional theory (DFT) to assess the binding energy of ethylene, water, and carbon monoxide on a set of more than 60 MOFs with open Cu sites in the form of Cu dimers. One useful observation from our results is that the relative binding energies of pairs of molecules (e.g., ethylene and water) can be calculated accurately from calculations that hold the MOF structure rigid and only relax the positions of the adsorbing molecules. These kinds of calculations are far more numerically efficient than calculations that relax all degrees of freedom in the system, so this observation will be useful in future efforts to screen larger collections ...

Competitive Binding of Ethylene, Water, and Carbon Monoxide in Metal–Organic Framework Materials with Open Cu Sites

Switchable Out-of-Plane Polarization in 2D LiAlTe2

Crystal lattice energy is a key property affecting the ease of processing pharmaceutical materials during manufacturing, as well as product performance. We present an extensive comparison of 324 force-field protocols for calculating the lattice energies of single component, organic molecular crystals (further restricted to Z' less than or equal to one), corresponding to a wide variety of force-fields (DREIDING, Universal, CVFF, PCFF, COMPASS, COMPASSII), optimization routines, and other variations, which could be implemented as part of an automated workflow using the industry standard Materials Studio software. All calculations were validated using a large new dataset (SUB-BIG), which we make publicly available. This dataset comprises public domain sublimation data, from which estimated experimental lattice energies were derived, linked to 235 molecular crystals. Analysis of pharmaceutical relevance was performed according to two distinct methods based upon (A) public and (B) proprietary data. These identified overlapping subsets of SUB-BIG comprising (A) 172 and (B) 63 crystals, of putative pharmaceutical relevance, respectively. We recommend a protocol based on the COMPASSII force field for lattice energy calculations of general organic or pharmaceutically relevant molecular crystals. This protocol was the most highly ranked prior to subsetting and was either the top ranking or amongst the top 15 protocols (top 5%) following subsetting of the dataset according to putative pharmaceutical relevance. Further analysis identified scenarios where the lattice energies calculated using the recommended force-field protocol should either be disregarded (values greater than or equal to zero and/or the messages generated by the automated workflow indicate extraneous atoms were added to the unit cell) or treated cautiously (values less than or equal to -249 kJ/mol), as they are likely to be inaccurate. Application of the recommended force-field protocol, coupled with these heuristic filtering criteria, achieved an root mean-squared error (RMSE) around 17 kJ/mol (mean absolute deviation (MAD) around 11 kJ/mol, Spearman's rank correlation coefficient of 0.88) across all 226 SUB-BIG structures retained after removing calculation failures and applying the filtering criteria. Across these 226 structures, the estimated experimental lattice energies ranged from -60 to -269 kJ/mol, with a standard deviation around 29 kJ/mol. The performance of the recommended protocol on pharmaceutically relevant crystals could be somewhat reduced, with an RMSE around 20 kJ/mol (MAD around 13 kJ/mol, Spearman's rank correlation coefficient of 0.76) obtained on 62 structures retained following filtering according to pharmaceutical relevance method B, for which the distribution of experimental values was similar. For a diverse set of 17 SUB-BIG entries, deemed pharmaceutically relevant according to method B, this recommended force-field protocol was compared to dispersion corrected density functional theory (DFT) calculations (PBE + TS). These calculations suggest that the recommended force-field protocol (RMSE around 15 kJ/mol) outperforms PBE + TS (RMSE around 37 kJ/mol), although it may not outperform more sophisticated DFT protocols and future studies should investigate this. Finally, further work is required to compare our recommended protocol to other lattice energy calculation protocols reported in the literature, as comparisons based upon previously reported smaller datasets indicated this protocol was outperformed by a number of other methods. The SUB-BIG dataset provides a basis for these future studies and could support protocol refinement.

Evaluation of Force-Field Calculations of Lattice Energies on a Large Public Dataset, Assessment of Pharmaceutical Relevance, and Comparison to Density Functional Theory.

The pressure effects and vibrational properties of energetic material: Hexahydro-1,3,5-trinitro-1,3,5-triazine (α -RDX)

Unfolding the chemistry of FOX-7: Unique energetic material and precursor with numerous possibilities

Accurate description of the non-covalent intermolecular interaction is significant for the study of energetic materials. Here, the performance of a variety of dispersion correction methods within d...

Assessment of dispersion correction methods within density functional theory for energetic materials

Uniaxial compression behavior and spectroscopic properties of energetic 1,1-diamino-2,2-dinitroethylene (FOX-7) crystals from density functional theory calculations

https://iopscience.iop.org/article/10.1088/1674-1056/27/5/056401/pdf

Compression behavior and spectroscopic properties of insensitive explosive 1,3,5-triamino-2,4,6-trinitrobenzene from dispersion-corrected density functional theory*

Zhaoyang Zheng

Papers

Assessment of dispersion correction methods within density functional theory for energetic materials

Uniaxial compression behavior and spectroscopic properties of energetic 1,1-diamino-2,2-dinitroethylene (FOX-7) crystals from density functional theory calculations

Compression behavior and spectroscopic properties of insensitive explosive 1,3,5-triamino-2,4,6-trinitrobenzene from dispersion-corrected density functional theory*

Uniaxial compression behavior and spectroscopic properties of the explosive pentaerythritol tetranitrate from first-principles calculations